Process for production of isoindolenine derivatives



United PROCESS FOR PRODUCTIUN OF ISOINDOLENTNE DERIVATW ES Georg Rtisch,Walther Wolf, and Heinrich Vollmann, Leverkusen, Germany, assignors toFarbenfabriken Bayer Aktiengesellschaft, Leverkusen, Germany, amanufacturing and trading organization of Germany No Drawing.Application September 4, 1952, Serial No. 307,903

Claims priority, application Great Britain August 25, 1949 12 Claims.(Cl. 260-2471) This application is a continuation-in-part of ourcopending application Serial No. 180,696, now Patent No. 2,727,043,filed August 21, 1950, entitled New Intermediate Products.

The present invention relates to new intermediate products and toprocesses for their production, in particular it relates to newphthalocyanine intermediates.

It is an object of the invention to provide new intermediate productswhich may be used for the production of phthalocyanines.

A further object of the invention is to provide new intermediateproducts which may be used for the production of phthalocyanines undergentle conditions, especially at lower temperatures.

A further object of the invention is to provide very reactive newintermediate products which may be utilized in the organic synthesis.

A still further object of the invention is to provide new methods forthe production of said new intermediate products.

Another object of the invention is to provide processes for theproduction of said intermediates on a technical scale.

Additional objects and features of this invention will become apparentas the following description proceeds. According to the prior artprocesses phthalocyanines have been produced by most various methodsfrom most various starting materials. Important starting materialsaccording to prior processes are, for instance, phthalic acid andphthalonitrile which are converted by the so-called urea-process or bythe so-called dinitrile-process into phthalocyanines.

It is supposed that the formation of phthalocyanines in the hithertoused processes passes various intermediates. However, extensiveexperiments carried out for determining the reaction mechanism havefailed to prove the presumed intermediates or to isolate them exceptmono-imino-phthalimide bined state and formulated this hypotheticalintermediate as follows:

atent Haddock expressly declares, however, that this intermediate or anyother intermediates of the phthalocyanine synthesis except theafore-mentioned mono-imino-phthalimide could neither be isolated nordetermined.

(A) It has now been found that such hitherto unknown intermediateproducts of the phthalocyanine synthesis are obtained by heatingo-arylene dicarboxylic acids, their nuclear substitution products orfunctional derivatives thereof in the presence of substances giving offammonia under the reaction conditions, for instance urea, as well as inthe presence of preferably at least equimolar amounts of anions whichare stable under the reaction temperatures, whereby preferably nitrateions are used and in case functional derivatives of o-arylenedicarboxylic acids containing carbonyl groups or these acids are used asreactants, in the presence of catalysts promoting forma tion ofphthalocyanine from o-arylene dicarboxylic acids and, if desired, in thepresence of inert solvents, to temperatures of about 200 C.

The intermediate products obtained according to the present inventionare believed to be derivatives of isoindolenine.

H Their constitution is as follows:

T1111 IfiIH o X N X NH M NE, NH resp.

in o X \N I;% R2N z wherein X stands for hydrogen or for a zero to fourorganic or inorganic radicals, for instance for alkyl radicals such asCH3, C2H5, C4H9, C5H11 etc., alkoxy radicals such as CH3O-, C2H5O- etc.,aroxy, alkyl mercapto and aryl mercapto radicals, heterocyclic radicals,further for halogen, NH acyl, NOz, COOH, SOsH, SO2NH2, SOzNH alkyl,SOzN(alkyl)z groups etc. X may also stand for one or two cyclic groupscondensed to the benzene nucleus of the isoindolenine. One or more ofthe carbon atoms of the carbocyclic nucleus or carbocyclic nuclei may bereplaced by hetero atoms for instance by one or two N-- or S-atoms. R1,R2 and R3 may stand for hydrogen or also for organic or inorganicradicals, for instance for alkyl radicals such as CH3, C2H5, C4H9,C8H17, C14H29 etc. These alkyl radicals may be substituted, for instanceby hydroxy groups etc., for cycloalkyl, aralkyl and for aryl radicalssuch as phenyl, substituted phenyl radicals, naphthalene oranthraquinone radicals, for other polycyclic radicals, for heterocyclicradicals and for acyl radicals, such as formyl, acetyl, benzoyl etc.Furthermore, R2 or R3 may stand for SOz aryl groups. R2+R3 may alsostand for an alkylene radical which may contain hetero atoms in itschain, for example the divalent radicals -(CH2)5 and (both free valencesbeing attached to the nitrogen atom). The radicals R1 and R2 (R3respectively) may form a cycloalkylene ring, for instance R1+Rz may beAs starting materials for the process according to the present inventionbesides phthalic acid and the functional derivatives thereof any oftheir nuclear substitution products containing the above mentionedradical X may be used. As polynuclear and heterocyclic o-dicarboxylicacids may be mentioned r1aphthalene-o-dicarboxylic acids,anthracene-o-dicarboxylic acids, pyridine-o-dicarboxylic acids,quinoline-o-dicarboxylic acids etc.

Of course, instead of the afore-mentioned .dicarboxylic acids theirfunctional derivatives may be used, such as, for instance, anhydrides,ammonium salts, imides, monoimino-imides, monoand diamides includingureides, o-cyanocarboxylic acids, whereby the carboxylic acid group maybe present in form of said functional derivatives, and o-dinitriles. Itis to be understood that the o-dicarboxylic acids, their nuclearsubstitution products or the :functional derivatives thereof which areknown as starting materials in the production of phthalocyaninesaccording to the prior art processes may .also be used as startingmaterials for the production of the ami-no-iminoisoindolenines accordingto the present invention.

When using dicarboxylic acids or-their functional derivatives containingcarbonyl groups as starting materials it is necessary to add a catalystfor carrying out the reaction. The same catalysts may find applicationwhich may be used in the production of metal phthalocyanines by theconventional methods, for instance, from phthalic anhydride, accordingto the sowcalled urea process. Especially suitable catalysts aremolybdic acid or its salts, for instance, ammonium molybdate. Onstarting from o-arylene dinitrile the addition of a catalyst may bedispensed with.

The term substances giving ofI ammonia means the compounds which may beemployed on carrying out the phthalocyanine synthesis according to theurea process. Such products are, for instance, urea, guanyl urea orbiuret which are used in excess.

For accomplishing the reaction according to the present invention it isfurther necessary to add such anions to the reaction mixture .as arestable under the reaction conditions applied. These are in the firstline anions of inorganic acids, such as, for instance, of nitric acid,phosphoric acid, sulfuric acid, hydrochloric acid, however, good resultscan also be attained by means of anions of organic acids, such as, forinstance, of aliphatic and aromatic sulfonic acids as well as vofmethane sulfonic acid, 'methionic acid, toluene sulfonic acid, and ofnaphthalenemonoand po'lysulfonic acids, for instance,naphthalene-1.S-disulfonic acid. These anions are to be used in at leastequimolar quantities referred to the dicarboxylic acids or theirfunctional derivatives. If minor quantities are employed the yield isgenerally reduced. Of course, larger quantities than the equimolar onesmay also be used without the yield being impaired thereby.

When using o-arylene dicarboxylic acids or their functional derivativescontaining carbonyl groups as reactants it is of advantage to usenitrate ions which yield with the corresponding1-amino-3-imino-isoindolenines insoluble, salt-like compounds which areless affected by changes of temperature. However, on using o-dinitrilesas starting material other anions yield equally good results. The saidanions are advantageously charged in form of their ammonium salts oralso as free acids which may be linked to the urea whereby it is of noconsequence whether the anions are added to the reaction mixture alreadybefore or after the beginning of the reaction. In the production of thenew intermediate products according to the present invention it isimmaterial whether the components are simply melted or whether a solventis added. In the first case, the substance giving off ammonia which ispreferably used in excess acts as diluent. In the second case, assolvents preferably higher boiling hydrocarbons or their substitutionproducts, such as, for instance, solvent naphtha, nitrobenaene, di' ortrichloro-benzene,

chloro-naphthalene are suitable, but also pyridine or quinoline may beused.

The reaction is generally initiated at temperatures of or above aboutC., i. e. temperatures at which the starting material generally beginsto melt. The reaction tem perature may be raised to the temperatureusually applied in the production of phthalocyanine according to theabove described process whereby ;reaction is completed within a shortperiod of time without ph'thalocyanines being formed thereby. Otherwise,the same conditions are applied which are customary in the production ofphthalocyanines according to the above-said urea process.

Methods to be applied for isolation of the aminoimino-isoindolenines ortheir salts obtained according to this process differ somewhat dependingupon whether the reaction has been performed with or without diluents.On working without diluents the melt is taken up with organic solvents,.for instance, acetone, alcohols, water or in mixtures thereof, and isfurther diluted with water. The salts of the amino-irnino-isoindoleninesalready precipitate if anions yielding difficultly soluble salts, suchas nitrateor ar-yl sulfonic acid anions were used for accomplishing thereaction. If, however, such anions were used .as give easily solublesalts of the amino-im ino isoindolenines, the amino-imino-isoindo1euinesare preferably precipitated by addition of nitrate ions inform of theirsalts or by addition of concentrated aqueous salt solutions, such asammonium chloride-, sodium chloride, or ammonium phosphate solutions.When the reaction has been accomplished in the presence of solventsisolation may be efiected by simply separating theamino-imino-isoindolenines from the solvents wherein theamino-immoisoindolenines in form of their salts are insoluble. They mayfurther be purified by means of solvents.

This process is described and claimed in our vcopending applicationSerial No. 180,696 of even date, entitled New Intermediate Products.

(B) The new intermediate products may also be obtained by adding ammoniaor its derivatives :to oar-ylene dinitriles .or the functionalderivatives of .o-aryllenedicarboxylic acids being free from carbonylgroups which may contain hetero atoms in the aromatic ring or to :thenuclear substitution products thereof, if desired, in the presence .ofsolvents and/or catalysts and/or nn dcr pressure.

Suitable starting materials for this reaction are besides phthalonitrileany of its nuclear substitution products containing the radicalXindicated in the above formula may be used. As polycyclic and:heterocyclic o-dinitriles may be named: naphthalene-o dinitriles,o-dicyano pyridincs, 2.3-.dicyano pyrazine .etc. Compounds containingfour .cyano groups are also suitable such as 1.2.4.5-.tetracyano-benzenc and 3.4.3'.4-tetracyano-diphenyl. It is 'to be understoodthat all dinitriles or functional derivatives of o-dicarboxylic acidsbeing free from carbonyl groups which are known as starting materials inthe production of phthalocyanines may also be used for producing the newintermediates according to the present invention.

According to this process suitable derivatives of ammonia are forinstance: primary and secondary amines such as methyl amine, dirncthylamine, ethyl amine, butyl amine, dodecyl amine, cyclohexyl amine, benzylamine, aniline, amino diphenyl, naphthyl amines, amino anthraquinon-esetc., substituted amines such as alkanolamines, substituted anilines andsubstituted naphthyl amines. ,Furthermore, sulfonamides such asp-toluene sulfonamide, heterocyclic nitrogen compounds such aspiperidine and morpholine, and N ,N -substituted "hydraz'ines such asN-amino-piperidine, N ,N -dipheny hydrazine may be used in the abovementioned reaction. Generally, the derivatives of ammonia are suitedwhich are stable under the reaction conditions. The addition of ammoniaor of said derivatives thereof to the aforementioned functionalderivatives of o-ary-lene diearboxylic acids being free from carbonylgroups, i. e. principally to the o-dinitriles, can be effected invarious manners. The temperatures applied in this reaction rarely exceedto 160 or 170 C. Thus, for instance, the said reactants may be treatedwith ammonia or its derivatives without any additions and in the absenceof solvents at temperatures above 100 C., preferably in the autoclave,under a pressure of up to about 120 to about 150 kg./cm. Aftercompletion of the reaction the excess of ammonia or derivatives thereofrespectively is removed. The reaction product thus obtained isamino-imino-isoindolenine in technically pure form which may directly beused or previously further purified by treating with water or organicsolvents. In order to facilitate purification it may be of advantage tocarry out the reaction in the presence of inert organic solvents, forinstance, of a low alcohol. Especially useful are alcohols containing atleast one -CH2OH group. On using a higher boiling solvent, for instance,polyvalent alcohols, it is not necessary to carry out the reaction inthe autoclave, but it is sufficient to dissolve the starting materialsin the autoclave and to pass ammonia or derivatives thereof in thegaseous state over or through the solution heated to temperatures fromabout 100 to about 160 C. if the ammonia derivative to be added has asufiiciently high boiling point, for instance, monoethanolamine, it issufficient to dissolve the starting material in this ammonia derivativeand to heat, for instance, to temperatures between 70 and 140 C. In thisway, the reaction proceeds practically quantitatively without furtheradditions being required.

The reaction may also be performed in the presence of anions which arestable under the reaction temperatures applied. The anions may becharged, for instance, in form of their ammonium or urea salts, such asammonium nitrate, ammonium chloride, ammonium phosphate and ureanitrate. in this case it is possible to carry out the reaction in thepresence of urea or ammonia. When processing in this manner thecorresponding salt of the lamino-3-imino-iso-indolenine is producedwhich may be purified as described in the foregoing.

If a catalyst is added, the reaction may also be accomplished at lowertemperatures. Suitable catalysts are heavy metal compounds, especiallythose which may be used for the production of phthalocyanines. Asexamples may be mentioned copper salts, especially salts of bivalentcopper and salts of cobalt, nickel, iron, cadmium, zinc, or alsoactivated metals, for instance, Raney-nickel. Also in this case, it isof advantage to carry out the reaction in the presence of a solvent and,especially, in the presence of monoor polyvalent alcohols, especiallyprimary alcohols. The said catalysts are added to the solution of thestarting material in quantities of about 0.150% calculated on thestarting material used and the solution is saturated with ammonia or itsgaseous derivatives mentioned above or a stream thereof is passed overthe solution. When using liquid or solid derivatives of ammonia thesemay be introduced into the solution. In this case, the addition ofspecial solvents may be dispensed with as, for instance, in the case ofmono-ethanolamine. The reaction mostly proceeds already at roomtemperature. The reaction results in the formation of the free basewhich mostly crystallizes from the solvent and may be separated in knownmanner. However, the base may also be isolated in form of its salts, forinstance, by addition of nitrate ions, or in form of its carbonate byintroducing carbon dioxide.

Besides the said heavy metal compounds also metal alcoholates orsubstances or mixtures acting like alcoholates or also alkali metalamides promote the addition of ammonia or the said derivatives thereofto the said functional derivatives of the o-arylene dicarboxylic acidsbeing free from carbonyl groups. However, on using these productscarehas to be taken that the reaction temperatures. are kept so low asto prevent the formation of phthalocyanine atall'or, at least, to amaterial extent, i. e. temperatures up to about C. are to be applied.Suitable metal alcoholates are those of alkali metals, alkaline-earthmetals and aluminium whereby the alcohol component may consist ofmonovalent alcohols of any chain length desired or also of polyvalentalcohols, such as glycols, glycerol. It is not absolutely necessary tocharge ready-made metal alcoholates but processing may also be performedunder conditions effecting the formation of alcoholates during reaction,for instance, when using alcohols together with the said metals or whenusing alkali metal amides together with an alcohol. However, the sameeffect is also attained by charging the said metal amides together withliquid ammonia or acid amides, such as formamide, acetamide. Mixtures ofalkali metal or earth alkali metal alcoholates and formamide may also beused. The amount of alcoholates or amides respectively required foraccomplishing the reaction may vary in a wide range. Thus, for instance,it is possible to obtain good yields with 1 per cent or less ofalcoholate calculated on the functional derivative of the o-arylenedicarboxylic acid being free from carbonyl groups. Similar yields areattained on using quantities corresponding to 1 mol of alcoholate per 1mol of the afore-mentioned derivative or quantities exceeding saidproportion.

Suitable solvents are in the first line the lower monoor polyvalentalcohols, such as, for instance, methyl-, ethyl-, propyl-, butyl-, oramyl-alcohol or glycol or, as already mentioned above, acid amides orliquid ammonia. The said solvents may also be used together withindifferent solvents miscible therewith. As examples may be mentionedaromatic hydrocarbons such as benzene and toluene, furthermoretetrahydrofuran or diethyl glycol.

On using the last-mentioned catalysts the optimum reaction temperaturesvary in a wide range and depend on the character of the metal-alcoholateor -amide and of the solvents or solvent mixtures used. On processingwith liquid ammonia the boiling temperature of ammonia is generallysuflicient to accomplish the reaction whereas in other cases the optimumreaction temperature is at about 40 to 65 C. However, it may hesometimes of advantage to process at temperatures up to or above 100 C.Care has to be taken that the upper limit of the reaction temperature isnot exceeded since in this case the formation of phthalocyanine takesplace. In spite of this fact, it is possible in some cases to operatewithin this critical temperature range if the reaction is performedWithin a very short time so that only 1- amino-3-imino-isoindoleninesare principally formed, i. e. if reaction is stopped before formation ofphthalocyanine starts or directly after starting of the dyestuffformation.

On using the said catalysts it is also possible to charge, besides thesaid arylene o-dinitriles, the corresponding hydrogenated dinitriles,for instance A-4,5-4-methyl tetrahydro-phthalonitrile. The correspondinghydrogenated 1-amino-3-imino-isoindolenines are thus obtained.

(C) When using the last-mentioned catalysts the process may be carriedout by reacting o-arylene dinitriles with the alcoholates in the absenceof ammonia or amines to form the corresponding l-alkoxy-derivatives ofthe 3- imino-isoindolenine which are described in the copendingapplication Serial No. 180,695 of even date, now Patent No. 2,683,643,relating to Process of Dyeing and Printing and reacting the1-alkoxy-3-imin0-isoindolenines thus obtained which may be monomeric aswell as condensed ones depending on the reaction conditions applied,after isolation or also in the reaction mixture with ammonia or theaforesaid derivatives of ammonia (see part B). The monomeric orcondensed a1- koxy derivatives may carry nuclear substituents which aredescribed in the above formula (see part A) under X. They may alsocontain hetero atoms in the carbocyclic ring ,and aromatic ringscondensed to the benzene nuearners c'leus. If ammonia or its gaseousderivatives are used for this reaction, the same are preferably passedthrough the solution of the *al'kox-y compounds in an inert organicsolvent, such as, for instance, benzene, acetone or in alcohol, or theammonia or the derivatives thereof are dissolved in alcohol and added tothe solution of the a-lkoxy compounds. However, salts of ammonia orderivatives thereof may also be used which are reacted with the allroxycompounds in form of their solutions. For accelerating the reaction itmay be sometimes of advantage to process in the presence of some waterin the reaction solution.

If monomeric alkoxy compounds are used for carrying out the reaction themonomeric amino-imino-isoindolenines are obtained. no-isoindolenines areemployed as reactants, condensed amino-imino-isoindolenines may beobtained, if the reaction is accomplished within a short time. Condensedamino-imino-isoindolenines comprise compounds wherein one carbon atomeach belonging to the heterocyclic nucleus of two molecules of theisoindolenine are connected by a nitrogen bridge and which may containalcohol as an addition. They correspond to the formula wherein X isdefined as in :the above formula of part A, 'Rx being CHs, Cal-I5,Cal-I7, C4H9 or CsHu and other .alkyl radicals and n being an integerfrom '1 to 6. If the ammonia or the amines are reacted for a prolongedtime and/or at higher temperatures, for instance up to about 160 (3.,the nitrogen bridge is split off and a further molecule of ammonia isadded so that, for instance, the case of the dimeric product twomolecules of monomeric amino-imino-isoindolenine are formed.

When using primary amines as derivative for carrying out the :abovereaction, also :the imino group of alkoxyimino-isoindoleni-ne may bereplaced by these primary amines.

Isolation of the amino-imino-isoindolenines thus obtained from thereaction solutions as far as they are crys tallized may be accomplishedin known manner by simply separating out. The non-crystallized portionsmay be isolated either after concentrating the solution, preferably invacuo, or by adding theaforesaid anions forming diflicultly solublesalts.

Besides the said alkoxy-imino-isoindlenines also the correspondingthio-compounds may be used for carrying out the reaction with ammonia orits above mentioned derivatives. Thus, for instance, according toPorter, Robinson and Wyler {Journal of the Chemical Society, London,1941, page 620) a mercapto compound is obtained which is indicated asocyano-thiobenzamide by addition of sodium sulfhydrate tophthalonitrile. The same compound may also be produced by reaction ofanhydrous sodium sulfide upon phthalonitrile in methanol. The productsprepared according to these two processes are believed to bel-mercapto-El-imino-isoindolenines. The correspondingamino-imino-isoindolenines are obtained by reacting the said mercaptocompounds or the alkyl ethers thereof with ammonium .nitrate in thepresence of a solvent or suspending agent and isolating the nitrates ofthe amino-imino-isoindolenine thus formed.

Instead of using the said alkoxy-imino-isoindolenines it is alsopossible to charge alcohol-hydrochloric-addi- :fiOH-LPIGdllCIS obtainedfrom aromatic o-dinitriles according :to 'Pinner (Die Imidoiither undihre Derivate, Berlin 1892, page lets.) which are almost identical withthe above-mentioned alkoxydmino isoindolenines except If, however,condensed alkoxy-imisoluble salts, for instance, nitrate ions.

8 that they contain hydrogen chloride in the molecule. Hence it followsthat in the reaction of the products obtained-according to 'Pinnerwithammonia or its derivatives which is preferably carried out in alcohol,care has to be taken that processing is done at very low temperatures,for instance, at 0 C. in order to avoid saponification by thehydrochloric acid present.

This process is described and claimed in our copending applicationSerial No. 307,905 of even date, entitled Process for the Production ofIsoindolenine Derivatives.

(D) In the production of the N-substituted derivatives ofarninodminodsoindolenines or its derivatives substituted in thecarbocylic ring as it is described in part A it is not absolutelynecessary to start from dinitriles or the above-mentioned reactants, butthese starting materials may also be reacted with ammonia to formaminoimino-isoindolenine which is not substituted at the nitro gen andthe products thus obtained or their salts respectively may be reactedsubsequently with the above mentioned derivatives of ammonia, forinstance primary or secondary aliphatic, aromatic, cycloaliphatic,polycyclic and heterocyclic amines, which may be substituted such asalkanolamines, the derivatives of aniline or naphthylamines etc., N .N-substituted hydrazines, furthermore piperidine, morpholine andhydroxylamine. This exchange reaction generally proceeds smoothly withsplitting olf ammonia. The reaction is most easily performed withprimary amines whereby the reaction velocity is often satisfactory atroom temperature. It is often of advantage to carry out the reaction inan inert organic solvent. Suitable solvents are in the first linealcohols, especially methanol or also water or formamide. When thereaction is accomplished by means of liquid amines, such as, forinstance, ethanol amine, anisidine, an excess of these products may actas solvent. In the case of primary amines either the amino group aloneor also the amino group and the imino group may be substituted. Theweakly basic aromatic amines, for instance, aniline substitute the aminogroup only when the reaction is performed under gentle conditions. Theimino group is substituted at higher temperatures and when the reactionis performed with a prolonged period of time. Mostly the reaction isaccomplished at temperatures up to about .and C.

On using strong basic, primary, aliphatic amines the exchange of theimino group is so easily efiected that generally derivatives substitutedat both nitrogen atoms can be isolated. On using secondary aminesderivatives are obtained which are substituted at one nitrogen only. Itis often possible to exchange the substituted amino or imino group viceversa by treatment with ammonia in excess against a non-substitutedamino or imino group.

It is further possible to replace a substituted amino or imino group byamino groups substituted by a diiferent radical. Also N-substitutionproducts which contain different substituents on the amino and iminogroup may be obtained. ,By using aliphatic diamines such aspolymethylene diamines products may be obtained in which both N-atoms ofthe amino and imino group are linked by a methylene bridge.

Isolation of the 1 amino-3-imino-isoindolenines thus obtained may beaccomplished in usual manner, for instance, by simply separating theportions crystallizing out of the reaction solution. In other cases theymaybe precipitated and separated by adding solvents reducing theirsolubility .and being miscible with the originally used solvent, forinstance, hydrocarbons or ice water. However, anions may be added whichyield difiicultly Finally, the l-amino-Sd-rnino-isoindolenines may alsobe obtained by distilling oil the solvent used in the reaction.

This process is described and claimed in our .copendingapplication-Serial No. 397,904 ofeven :date, now Patent No. 2,739,156,entitled Process for the Production of Isoindoleine Derivatives.

(E) The new intermediate products are also obtainable by producing theyellow to red colored complex compounds containing copper from o-arylenedicarboxylic acids, which may also contain hetero atoms in the aromaticnucleus, or their nuclear substitution products capable of formingphthalocyanine or their functional derivatives which comprises heatingsaid o-arylene compounds with copper salts and substances giving offammonia. Thereupon the complex compounds thus obtained which containmore than one atom of copper per one o-arylene radical are treated attemperatures up to about 30 C. with agents capable of dissolvingmonovalent copper directly or after converting same into the bivalentstate. The treatment of the said complex compounds is preferablyeffected with nitric acid whereby advantageously during this treatmentor subsequently anions are added which yield difiicultly soluble saltswith the aminoimino-isoindolenines obtained according to the presentinvention.

Complex compounds containing more than one atom of copper per oneo-arylene radical obtained from o-arylene dinitriles and copper salts inthe presence of substances giving off ammonia at elevated temperatureshave already been known. Their production is accomplished in mostvarious ways whereby compounds are obtained which depending upon thereaction conditions applied differ in their outer appearance, especiallyin color as well as in their physical and chemical properties, forinstance, solubility and reactivity. They may be more or less easilysoluble or also insoluble in high boiling solvents, for instance,quinoline. However, all these compounds are characterized in that theycontain more than one atom of copper per one o-arylene radical and thatthey yield the above-described new intermediate products of thephthalocyanine synthesis by treatment with agents dissolving monovalentcopper directly or after converting same into the bivalent state.

The preparation of these copper complexes has been described, forinstance, in FIAT Final Report 1313, vol. III, pages 342, 344, 345.According to this citation they are obtained as difficultly soluble toinsoluble substances from phthalonitrile and cuprous chloride or cuprousbromide whereby more than one mol of the cuprous salt calculated on onemol of phthalonitrile is used. The mixture of phthalonitrile and thesaid cuprous salts is heated in the presence of urea and formamide attemperatures up to about 180 C. They may be obtained quite generallyfrom o-arylene dinitriles and copper salts in the presence of urea orformamide at about the same temperatures. The reaction may be carriedout in the presence of solvents, for instance, nitrobenzene orchlorobenzene. However, on using high boiling solvents, for instance,quinoline, it is not necessary to add substances giving 01? ammonia, forinstance, urea or formamide but ammonia may be added in its gaseousform. Suitable reactants for the production of the insoluble coppercomplex compounds are besides o-dinitriles, the correspondingo-dicarboxylic acids, their nuclear substitution products or also thefunctional derivatives thereof described heretofore. In case thestarting materials contain carbonyl groups, the above describedcatalysts used in the production of phthalocyanine according to the saidurea process, for instance, ammonium molybdate and molybdic acid have tobe added. The optimum reaction temperatures may be varied between 140and about 220 C. Instead of using the above-said cuprous chloride orcuprous bromide also other copper salts may find application, forinstance, copper nitrate or copper acetate. In all cases the difficultlysoluble to insoluble copper complexes are obtained provided that morethan 1 mol of the copper salt per one mol of the o-arylene dicarboxylicacid or the functional derivatives thereof is used. Hence it followsthat copper salts not dissolving in the reaction medium under thereaction conditions applied or only to an immaterial extent shall not tobe used if possible since otherwise the quantity of dissolved coppersalts in the reaction mixture may be too small and the correspondingphthalocyanines may be formed. In this connection a process for theproduction of copper complexes may be mentioned according to which thecomplex compounds may be obtained at room temperature or only slightlyraised temperature. This process is carried out, for instance, bydissolving arylene dinitriles in a lower alcohol, for instance, methanoland introducing gaseous ammonia after adding an excess of cuprouschloride (more than one mol of cuprous chloride per one mol ofo-dinitrile). When using other solvents than alcohol which at leastslightly dissolve the copper compounds in combination with the ammoniaintroduced, such as, for instance, ketones or tertiary amines, it isoften necessary to process at higher temperatures. In this case it mayalso be neces-- sary to apply the ammonia under pressure. Ammonia: mayalso be replaced by its salts. As copper salts may be; used, besides thesalts of monovalent copper, the salts of bivalent copper or thehydroxide of bivalent copper. Thecomplex copper compounds obtained bymeans of bivalent: copper compounds are mostly blue-grey colored.

Decomposition of the complex copper compounds is; eifected as alreadymentioned with agents capable of dis-- solving the complex-combinedcopper whereby the com plex is destroyed. On the other hand, theseagents shall. not saponify the 1-amino-3-imino-isoindolenines formed...For this purpose, mineral acids and alkali cyanides have:

proved to be most suitable. On using mineral acids proc essing ispreferably carried out with anhydrous acids in. order to avoidsaponification of the new intermediateproducts, and at very lowtemperatures, i. e. preferably while cooling with ice, or the mineralacid is added int quantities only so that towards the end of thereaction: the mixture shows no longer a mineral acid activity;Saponification of 1-amino-3-imino-isoindolenines is es-- peciallyprevented or reduced by the presence of anions yielding insoluble saltswith the isoindolenines. Anions suitable for this purpose are, forinstance, those of nitric acid and of aryl sulfonic acids. Herefrom theparticular advantages of the application of concentrated nitric acid fordecomposition are given. By observing the abovementioned conditions goodyields are also obtained by means of concentrated sulfuric acidcontaining some sulfur trioxide, or with mixtures of strong mineralacids with anhydrous organic acids. When the acid shows no oxidizingeifect it has proved to be of advantage for achieving a smooth and fastreaction to add oxidizing agents, such as hydrogen superoxide, ororganic or inorganic peracids. When using acids which do not yieldinsoluble salts with the amino-imino-isoindolenines it is advisable forthe above-said reasons to add the anions forming difiicultly solublesalts, for instance, salts of toluene sulfonic acid, naphthalenesulfonic acid or naphthalene disulfonic acid or also nitrate ionsalready during decomposition. However, if decomposition is effected bymeans of alkali cyanides, it is not necessary to add the aforesaidanions since the l-amino-3-imino-isoindolenines formed in the alkalinereacting alkali cyanide solution are present in form of free bases whichare diflicultly soluble therein and immediately crystallize. Therebythey are substantially prevented from being saponified by the alkalinesolution. Suitable cyanides are in the first line potassium and sodiumcyanide which are preferably used in form of their aqueous solutions.Cyanides have to be added at least in such quantities so as to becapable of forming the corresponding complex alkali copper cyanidecompounds with the dissolved copper ions.

Isolation of the difiicultly soluble salts of 1-amino-3-imino-isoindolenines thus obtained may be accomplished by simplyseparating out. A preferred method of execution consists, for instance,in pouring after decomposition of the copper complex compounds themineral acid solutions onto ice or in diluting these solutions withwater with good stirring, the difiicultly soluble salts ofLamino-S-imino-isoindolenines immediately precipitating thereby. If theabove-said anions are not added during decomposition'1-amiuo-3-imino-isoindolenines may be precipitated by subsequentaddition of these anions, if necessary, after neutralization of themineral acids from the aqueous solutions. Precipitation may beaccomplished, for instance, by adding to the ice-water into which theconcentrated acid is introduced, at least the equivalent amounts ofalkalies, such as ammonia, alkali lye, alkali carbonate or bicarbonate,for neutralizing the acid. If decomposition is effected with alkalicyanides the l-amino- 3-imino-isoindoleuines crystallizing may be easilyseparated in known manner after complete decomposition of the complexes.

This process is described in and claimed by our copending applicationSerial No. 307,906 of even date, entitled New Intermediate Products.

The amino-imino-isoindolenines obtained according to the above describedprocesses represent new products. They are generally colorless to yellowcolored and mostly readily crystallize. They are stable and fast tostoring in their crystalline form. Their melting points are generallyabove 100 C. On melting, in most cases, splitting off of ammonia or thederivatives thereof and decomposition take place, colored melts beingleft thereby.

The amino-imino-isoindolenines partly dissolve in water and in alcoholsto form the corresponding hydrates or dihydro-alkoxy-derivatives, i. e.they absorb one mol of water or alcohol. Furthermore, they are solublein dilute and in concentrated acid from which they may be recovered inform of their salts. These salts are more or less soluble in Water, suchas, for instance, the formates, acetates and chlorides; difiicultlysoluble are, for instance, the nitrates, sulfites, phosphates, oxalatesand the aryl sulfonic acid salts. The salts ofamino-imino-isoindolenines wherein nitrogen is substituted often behavedifferently as to their solubility from the unsubstituted ones. Thesalts when heated are also soluble in a number of organic solvents, suchas in substituted aromatic hydrocarbons, such as nitrobenzene,chlorobenzene and acid amides, furthermore in tertiary bases, forinstance, pyridine. Also in this case, decomposition, i. e. splittingoil? of ammonia or derivatives thereof mostly takes place. The salts aregenerally difiicultly soluble in aliphatic and aromatic hydrocarbons aswell as in ketones, ethers etc. With dilute alkali lyes the hydrates orthe free base respectively form alkali metal salts being easily solublein water.

The l-amino-3-imino-isoindolenines are gradually saponified in aqueoussolutions, the corresponding monoimino arylene dicarboxylic acid amidesbeing formed thereby. Decomposition is promoted by heating or addingdilute acids or alkalilyes.

The salts of l-amino-3-imino-isoindolenines generally contain one acidresidue per one mol of isoindolenine however, salts have been isolatedcontaining less, for instance, or /3 equivalent of the acid per 1 mol ofisoindolenine-which is mostly present in a combined state, for instance,in the case of nitrate. The salts may also be recrystallized fromaqueous ammonia solutions under certain conditions. On the other hand,in any case, the free base or its hydrate respectively is obtained byadding equivalent amounts of alkali lye to the salts.

The l-amino-3-imino-isoindolenines, as far as their amino group is notsubstituted, are accessible to many reactions of the primary amines. Forinstance, they may be acylated or alkylated. With diazouium compoundsthey yield diazo-amino compounds. They can easily be reacted withaldehydes. Aromatic o-dinitriles may be added in the presence of alkalimetal alcoholates to form higher molecular products mostly containingalkoxy groups in the molecule. The l-amino3-irnino-isoindolenines areconverted with phenyl hydrazine into intensely- 12 isoindolenines inhigh boiling solvents for a longer time ammonia or, if N-substitutedcompounds have been used, the derivatives thereof are split off andcondensation products are obtained which contain i. e. tricyanocyaphenine. On heating the 1-amino-3-imino-isoindolenines inpyridinewater-mixtures in the presence of sodium hydrosulfite generallyblue colored solutions are obtained which by the action of excess sodiumhydrosulfite or atmospheric oxygen easily decolorize again.

On heating solutions of amino-imino-isoindolenines with reducing agents,for instance, with formaldehyde or if reducing agents are used as asolvent, for instance, formamide, more or less large quantities ofmetal-free phthalocyanines are obtained. On heating them together withmetal salts and reducing agents the corresponding metal phthalocyaninesare formed.

The monomeric as well as the condensed aromatic 1-amino-3-imino-isoindolenines may be reacted with heavy metals formingcomplexes, if necessary, in the presence of solvents to formcrystallizable complexes.

The 1-amino-3-imino-isoindolenines according to the presentinvention maybe substituted as already mentioned above in the carbocyclic ring by oneor more radicals. The compounds may also carry condensed aromatic orheterocyclic nuclei.

Besides the nuclear substituents the compounds may carry at the nitrogenof the .imino and amino group the most various organic substituents.

The new 1--amino-3-imino-isoindolenines-as far as they contain in theamino group an active hydrogen atom in a combined statemay be present intheir tautomeric forms, i. e. a hydrogen atom is attached to thenitrogen bridge; in this case the 1-amino-3-imino-isoindolenines showthe constitution of the corresponding diirninoimides. In some cases,however, other tautomeric forms may also be present.

The invention is further illustrated by the following examples withoutbeing restricted thereto, the parts being by weight.

Example 1 7.0 parts by weight of 2'.5-dimethoxy-diphenyl-3.4-dicarboxylic acid anhydride, 25 parts by weight of ammonium nitrate, 0.2parts by weight of ammonium molybdate are introduced in portions into amelt of .75 parts by weight of urea while stirring at 140 C. Thetemperature is slowly raised to 170 C. After 1-2 hours a yellowprecipitate forms in the orange colored solution. The stiffening melt isdiluted by addition of urea so as to remain capable of being stirred.After 6 hours 500 parts by volume of cold water are added to the meltwhich is cooled to C., the yellow precipitate of the resulting nitrateof 1amino-3-imino-5-(or 6-)-(2.5--dimethoxy-phenyl)-is0indo1eninc issuction filtered, washed with cold water and dried. The yield amounts to70 parts by weight.

The base is prepared by mixing with stirring 70 parts by weight of thenitrate and parts by weight of methanol, adding a solution of 4.8 partsby weight of sodium in 100 parts by volume of methanol, separating thesodium nitrate by filtration and distilling off the methanol in vacuo.The base remains behind as a yellow crystalline mass in a quantitativeyield.

Example 2 128 parts of phthalonitrile are melted with 240 parts of'ureaand 80 parts of ammonium nitrate and stirred for is sucked off andwashed with water. The product is obtained in excellent yield andpurity.

Example 3 Example 4 25 parts of 4-phenoxyphthalic acid are introduced at110 C. into a melt of 12 parts of urea, 14.4 parts of ammonium nitrateand 0.3 parts of ammonium molybdate and stirred for one hour at 175-180C. until the initially formed long, thin prisms have been converted intoshort, coarse crystals whereby a mixture of 12 parts of urea and 12.4parts of ammonium nitrate is still gradually added. The cooled melt isdiluted with methanol and water, the precipitated nitrate of 5- or6-phenoxy-lamino-3-imino-isoindolenine respectively is sucked off andwashed with methanol and water. If any mono-iminophthalimide is presentin the nitrate it is removed by boiling oft" with acetone.

The free base is obtained from the nitrate by introducing same into asolution of sodium methylate in acetone, the base dissolving thereby.The base is precipitated from the solution by adding water.

The 5-(or 6-)phenoxy-l-amino-3-imino-isoindolenine melts at 99 C. and isvery easily soluble in methanol and, contrary to mostamino-imino-isoindolenines, also soluble in acetone. The productdissolves in dilute acetic acid with weakly yellow coloration. By addingammonium nitrate and acetic acid the product is precipitated from itssolution in acetone in form of its difficulty soluble nitrate incolorless, clustered needles.

Example 5 116 parts of 4.5-diphenyl-phathalic anhydride are introducedat 110 C. into a melt of 5 parts of urea, 6 parts of ammonium nitrateand 0.1 part of ammonium molybdate and heated for one hour each at 140C. and 155- 160 C. and for further 14-15 hours at 175180 C. until theinitially formed long, thin needles have been converted into small,coarse crystals. The melt somewhat cooled on standing is diluted withmethanol, the nitrate of 5.6-diphenyl-l-amino-3-imino-isoindolenine issucked off and washed with methanol and acetone. The best method ofisolating the free base consists in treating the nitrate with a solutionof sodium methylate in dioxane.

Example 6 60 parts of urea, 55 parts of 3-chlorophthalic anhydride, 48parts of ammonium nitrate and 0.5 part of ammonium molybdate are heatedand worked up according to the method described in Example 14 ofprovisional specification, British Patent 698,049. 41 parts of thenitrate of 4- or 7-chloro1-amino-3-imino-isoindolenine respectively arethus obtained.

Example 7 A mixture of 56 parts of 4-phenylphthalimide, 60 parts ofurea, 40 parts of ammonium nitrate and 0.3 part of ammonium molybdate isheated with stirring to 170 C. until the melt has become crumbly.Heating is then continued at the same temperature without stirring.After heating for totally 20 hours the cold melt is stirred withmethanol, sucked off, the reaction product is washed with methanol anddried. 65 parts of the technically pure nitrate of1-amino-3-imino-5-phenylisoindolenine or of1-amino-3-imino-6-phenylisoindolenine are thus obtained.

Example 8 128 parts of phthalonitrilc, 300 parts of urea and 125 partsof urea nitrate are stirred for several hours at about 150 C.

Further processing and isolation of the reaction product is performed asdescribed in Example 2.

Example 9 204 parts of 3.4-dicyano diphenyl are added to a meltconsisting of 480 parts of urea and parts of ammonium nitrate andstirred for 30 hours at 150-160 C.

The cooled melt is ground with a solution of ammonium nitrate in waterand acetic acid is added until the reaction has become neutral or Weaklyacid. The mixture is then sucked off and the product is washed withWater. The phenylamino-imino-isoindolenine is obtained in a very purestate and excellent yield.

Example 10 calculated for:

Example 1 1 32 parts of phthalonitrile are heated with 95.6 parts ofliquid ammonia in a stirring autoclave of chrome-nickelsteel for 5 hoursat 118 C. (about 80 atmospheres overpressure). After cooling the NHs isblown off and the solid, light blue-grey residue (37.6 parts) is groundseveral times with water previously heated to 4050 C. and sucked offuntil the residue has no longer a bitter taste. For removing any slightamounts of phthalonitrile the residue is boiled oil with water, about1.5 parts of deep blue small needles of practically metal-freephthalocyanine remaining behind thereby. The aqueous extract solidifieson cooling to a viscous paste of colorless small needles ofamino-imino-isoindolenine which after sucking off, cautiously washingwith some water and drying, melt at 192-195 C.

Example 12 128 parts of phthalonitrile are heated to C. with 80 parts ofammonium nitrate in 4000 parts of liquid ammonia while stirring for 20hours in an autoclave.

The crude amino-imino-isoindolenine-nitrate remaining after distillingoff the ammonia is purified by treatment with cold water and hotbenzene.

Example 13 isolation the reaction mixture may be diluted with a sol 75vent, for instance, an alcohol.

15 Example 14 128 parts of phthalonitrile are mixed with stirring with250 parts of glycol and the mixture is saturated with ammonia at 50 C.The dinitrile dissolves during about 24 hours whereas the glycolate of1-amino-3-imino-isoindolenine (CsHvNs-l-CzI-IrOz) crystallizes. Theglycolate is isolated by suction filtration at C., washed with benzeneand acetone.

When using in the above reaction starting materials containingcontaminations the mixture is heated to about 80 C. towards the end ofthe reaction whereby the reaction product dissolves and thecontaminations can easily be separated off by filtration.

The reaction may also be conducted at higher temperatures, .say up toabout 120 C. In this case it is preferable to dissolve the dinitrile inglycol and to add ammonia at decreasing temperatures.

The reaction proceeds in the same manner below 50 C., however, thereaction times are prolonged in the absence of catalysts such as alkaliand metallic ions.

Example 16 parts of phthalonitrile are dissolved in 50 parts of glycolat 130140 C. and while passing ammonia over the mixture stirred for 2-3hours each at 120130 C.,

100-110" C., 8090 C., 50-60 C. and finally at 0 C. with cooling.

The molecular compound of amino-imino-isoindolenine with glycolCsH7N3.C2HsO2 crystallizes in abundant quantity in analytically pureform and may be easily isolated by sucking oil and washing with acetone.

Example 16 Example 17 50 parts of phthalonitrile and 0.5 part of coppersulfate are suspended in 250 parts of methanol and the rruxture issaturated with ammonia. Phthalonrtrile gradually dissolves at 2070 C. Ablue-grey, finely crystalline copper complex salt ofamino-imino-isoindolenine precipitates. Moreover, parts of the free baseCal-[1N3 precipitate in coarse crystals. The chief portion remainingdissolved can be precipitated as nitrate by stirring the mixture intoweakly acidified water containing nitrate. A quantitative total yield isobtained.

The reaction proceeds more slowly in formamide, however, may equally beperformed in other alcohols, such as ethanol, glycol. Similar or betterresults are attained on replacing CuSO4 by other copper salts, such asCuCl, CuClz, 2H2O, CuNOgBl-IzO, glycocoll copper, acetylacetone-copper,or also salts of copper, nickel, cobalt, cadmium etc., or active metals,for instance, Raney-nickel. Depending on the conditions applied thereaction is accomplished within 2-70 hours.

Example 18 A sodium methylate solution consisting of 3 parts of sodiumand 128 parts of anhydrous methanol is poured onto 128 parts ofphthalonitrile.

The mixture is vigorously stirred with cooling however, towards the endof the reaction which is accomplished within a few minutes thetemperature is allowed to raise up to 50 C. or also up to the boilingpoint of the mixture. The color of the mixture changes thereby fromyellow to orange and finally to deep dark red brown. As soon as thephthalonitrile has completely dissolved the temperature is reduced below50 C. and gaseous ammonia is passed over the solution with stirring.After some time l-amino-3-imino isoindolenine begins to precipitate asthick crystal paste. The mixture is further stirred for some hours,diluted with 128 parts of acetone, further saturated with ammonia, thetemperature is lowered to 0 C., the solution is sucked ofi, theprecipitate is washed with acetone until the washing has becomecolorless, and dried.

to parts of 1-amino-3-imino-isoindolenine corresponding to 70% of thetheoretical are thus obtained. The product is yellowish colored. Acompletely colorless product is obtained by carrying out the reaction atlower temperatures with one and a half to two times the quantity ofalcohol and three to five times the quantity of sodium, the yield beingsomewhat impaired thereby.

The portions of the reaction product remaining dissolved after suckingoff and washing may be precipitated as nitrate.

Example 19 50 parts of sodium are dissolved in 320 parts of anhydrousethyl alcohol. The mixture which solidifies after cooling is dissolvedin 1130 parts of formamide. At 50 C. 204 parts of 3.4-dicyano diphenylare introduced with stirring until after a few hours the dinitrile hasdissolved. The reaction mixture soon solidifies to a crystal paste whichis cooled and kept at room temperature for several hours. Theprecipitated product is separated by suction, the part remainingdissolved is precipitated by adding water. The monohydrate of l-amino-S-imino-S-(or 6)-phenyl-isoindolenine is obtained in excellent purityand yield from both parts by recrystallization from a mixture of acetoneand water (about 1:1).

Example 20 40 parts of calcium are dissolved in 400 parts of anhydrousmethanol. 1130 parts of formamide are added at room temperature,whereupon 128 parts of phthalonitrile are introduced.

The solution is stirred for a few hours at 70-80" C. The initiallyyellow solution which changes to yellow green is introduced when coldinto a mixture of ice, ammonium nitrate and nitric acid. The precipitateformed thereby is sucked oil and washed with water. After drying thecrude product is boiled out with acetone and sucked ofi again. Thenitrate of the amino-imino-isoindolenine thus obtained is .not yet quitepure. Purification may be achieved as indicated in Example 13.

Reaction may also take place without the use of alcohol in such a mannerthat the calcium is dissolved in formamide at temperatures of about 70C. and the phthalonitrile is introduced with stirring after cooling.

When working in this manner the possibility of dyestufll formation beinginitiated is much greater.

Example 21 Example 22 46 parts of sodium are dissolved in 800 parts ofa'nhydrous methanol and after cooling there are introduced with stirring128 parts of phthalonitrile dissolving with slight self-heating. Intothe mixture is stirred a solution of 342 parts of p-toluene sulfonaniidein 800 parts of anhydrous methanol and the mixture is heated for 4 hoursat about 90 C. The l-p-toluene sulfonarnino-3-iminoisoindolenine is thusformed.

By stirring the reaction mixture into an ammonium salt solution cooledwith ice the reaction product pre- 17 cipitates. The precipitate ispurified by boiling out with ethanol and with benzene. This sulfonarnidecompound does not form a diflicultly soluble nitrate.

Example 23 128 parts of phthalonitrile are introduced into a mixture of86-90 parts of piperidine and a sodium methylate solution consisting of2 parts of sodium and 45-50 parts of methanol.

The phthalonitrile dissolves within a very short time. The heat beingset free is discharged to such an extent that the temperature raisesonly to about 50 C.

The 1-piperidino-3-imino-isoindolenine precipitates in in colorlessneedles already at the reaction temperature or after cooling. Isolationis effected by diluting the reaction mixture with 80100 parts ofacetone. The mixture is sucked off when cold and the precipitate iswashed with cold acetone and benzene. The product obtained isanalytically pure and shows a flash point of 120 C.

On replacing piperidine by morpholine the reaction yields1-morpholino-3-imino-isoindolenine. The product decomposes at about 140C. with blue coloration. It forms with ammonium nitrate1-amino-3-imino-isoindolenine nitrate.

Example 24 46 parts of sodium are dissolved in 800 parts of anhydrousethanol. 430 parts of piperidine are added and 204 parts of 3.4-dicyanodiphenyl are dissolved in the mixture with stirring and heating.

The solution from which impurities, if any, may be removed by filtrationis heated for 2-3 hours at about 90 C. and then cooled. The reactionmixture from which on longer standing small amounts of the base formedprecipitate is then stirred into a mixture of ice and 200 parts ofnitric acid. The nitrate of the S-(or 6-)-phenyl-l-piperidino-3-imino-isoindolenine is thus obtained in goodyield. The precipitate is sucked 01f, washed with water and dried. Theproduct may be recrystallized from an alcohol-benzene-mixture (about1:1). The nitrate melts at about 215220 C. with dark coloration.

According to elementary analysis the compound exhibits the followingcomposition:

calculated for: found Cw 2u0s 4 Percent Percent =64. 05 0 =64. 74 H= 4.20 H= 5. 72 N=15.85 N=15. 91 O=14. 28 O=l3. 63

By replacing piperidine by morpholine, aniline, dimethylamine wellcrystallized compounds are obtained in good yields.

Example 25 calculated for: found CrzHmOaNl Percent Percent C=55.22 054.51 H= 6.44 H= 6.11 O=18.20 0:18.17 N=21.20 N=2l.21

18 Example 26 parts of pulverized sodium amide are introduced into 850parts of formamide in portions at 0 C. while stirring and cooling with afreezing mixture of ice and sodium chloride. 128 parts of phthalonitrileare added in portions to the clear solution and the temperature israised to 60-70 C. A yellow solution is obtained from which colorlessprismatic needles precipitate.

After 6-8 hours the solution is cooled, the amino-iminoisoindolenineobtained in good yield is sucked off, washed with some formamide andacetone and dried. By introducing the filtrate into a mixture of ice andnitric acid containing as much nitric acid as is required forneutralization and salt formation, a further quantity ofaminoirnino-isoindolenine is obtained as nitrate.

Example 27 80 parts of pulverized sodium amide are introduced inportions at 0 C. into 1130 parts of formamide while stirring and coolingwith a freezing mixture of ice and sodium chloride. 204 parts of3.4-dicyano diphenyl are gradually added to the solution. Thetemperature is then slowly raised to 50 C. A yellow solution is formedfrom which grey crystals precipitate. After about 6 hours the solutionis cooled, the hydrate of phenyl-amino-iminoisoindolenine obtained inalmost quantitative yield is sucked ofi, washed with some formamide andacetone and dried.

Example 28 12.2 parts of sodium amide are introduced into 150 parts offormamide at 0 C. with cooling and stirring. 30 parts of4.S-dichlorophthalonitrile are added in portions to the clear solution.After gradually raising the temperature to 40 C. and stirring at thistemperature for 12 hours the mixture is cooled and sucked off, theprecipitate obtained is washed with acetone and ether and dried. Theyield amounts to 27 parts of 4.5-dichloro-1-amino-3- imino-isoindoleninedecomposing at about 265 C. While splitting 01f ammonia.

Example 29 60 parts of formamide, 3.5 parts of sodium amide and 107parts of 3.4-dicyanodiphenylsulfone are reacted as described in Example29. 9 parts of 1-amino-3-iminoisoindoleninyl-S- or -6-phenylsulfonedecomposing at about 215 C, while splitting off ammonia are thusobtained.

Example 30 32 parts of pulverized sodium amide are introduced inportions into 320 parts of formamide at 0 C. with stirring and coolingwith a freezing mixture of ice and common salt. 53 parts ofA-4.5-4-methyl-tetrahydrophthalonitrile are added in portions to theclear solution.

The temperature is allowed to raise to room temperature, wherebycolorless crystals more and more precipitate from the initially yellowand then violet red colored solution. After about 12 hours tetrahydratedaminoimino-methyl-isoindolenine formed is sucked oil and washed withacetone and ether. The product decomposes at about 130 C. whilesplitting off ammonia.

The new substance is converted into the correspondingtetramethyloctahydrometal-phthalocyanine by means of metal salts, forinstance, salts of copper, nickel and cobalt, in the presence of glycolor formamide, already at temperatures of about C. The new phthalocyaninedissolves in concentrated sulfuric acid with blue coloration. On gentlyheating the blue solution changes to brown,tetramethyl-copper-phthalocyanine being formed with furtherdehydrogenation.

If, however, the tetrahydrogenated amino-imino-methylisoindolenine isheated in nitrobenzene in the presence of a copper salt for a longertime tetramethylcopper-phthalocyanine is immediately obtained.

Example 31 15.6 parts of sodium amide are dissolved at C. with coolingand stirring in 90 parts of formamid. 17.8 parts ofl.2.4.5-tetracyanobenzene (prepared from pyrromellitic acid tetraamideby conventional methods) are added in small portions to the clearsolution. A deep red solution is formed from which yellow, prismaticneedles soon precipitate which are sucked off after one hours stirringat room temperature, washed with some formamide and acetone and dried.The benzodi(amino-iminopyrrolenine) obtained in good yield decomposes onheating without melting.

Example 32 40 parts of sodium amide are dissolved at 0 C. in 300 partsof formarnide with stirring. 60 parts of 3.3'.4.4- tetracyanodiphenylare added in portions to the clear solution and gradually heated to 4060C., a yellow brown solution being formed thereby. After about one hoursstirring the solution is cooled with ice.Di(amino-iminoisoindoleninyl)precipitates in nearly quantitative yieldin yellow, fine, small needles, which are sucked off, washed with someformamide and acetone and dried. Di(aminoimino-isoindoleninyl)decomposes on heating without melting.

Example 33 64 parts of phthalonitrile are dissolved at 10 C. in 2000parts of anhydrous benzene and 23 parts of absolute alcohol are added.Thereupon dry hydrogen chloride is passed over the mixture at -10 C. for48 hours and the crystalline precipitate is sucked off, washed with drybenzene and dried in vacuo. The yield amounts to 63 parts.

' 40 parts of the imino-ether thus obtained are introduced at 0 C. intoa solution of 50 parts of ammonia in 400 parts of methanol and themethanol is evaporated in vacuo.

44. parts of a residue which is dissolved at 0 C. in 200 parts of about80% nitric acid are obtained. On pouring the solution onto small piecesof ice the nitrate of l-a.mino-3-imino-isoindolenine is precipitated,sucked ofi, washed with water and dried in air.

Replacing phthaloni'trile by the equivalent quantity of3..4-dicyanodiphenyl the nitrate of 1-amino-3-imino-5-(or-6-)phenylisoindolenine is obtained.

Example 34 102.4 parts of phthalonitrile are introduced at 20 C. into asolution of 4.6 parts of sodium in 81 parts of methanol diluted with 450parts of benzene.

Stirring'is continued until the phthalonitrile has been dissolved withyellow coloration. Thereupon 20.4 parts of ammonia (100%) dissolved inmethanol and 0.9 part of water are added and it is further stirred at 20C. until a test portion gives no longer a stable, blue leuco compound inmethyl alcoholic aqueous solution with dilute sodium hydroxide solutionand sodium hydrosulfite. 64.4 parts of formic acid are allowed'to runinto the solution which is still stirred for some time; the crystallineprecipitate formed is sucked oil, washed with benzene and dried invacuo. About 167.7 parts of formate corresponding to 94.5 parts of1-amino-3-imino-isoindolenine or 85.6% of the theoretical are thusobtained.

By replacing formic acid by equivalent amounts of other carboxylic acidscorresponding salts of the acids are obtained.

Example 35 35.6 parts of LZ-dicyanonaphthalene are introduced into asolution of 1.15 parts of sodium in 40.4 parts of methyl alcohol dilutedwith 182.5 parts of benzene and stirred until the 1.2-dicyanonaphthalenehas been dissolved with yellow coloration. Thereupon 20.4 partsv of.ammonia (100%) dissolved in methanol are added and stirred until a testportion gives-no blue leuco compound.

in methyl-alcoholic, aqueous solution. The precipitateobtained in, agood yield (amounting to 70% of the theoretical) is sucked off andwashed with benzene and ligroin and dried in vacuo. The crude product isobtained by concentrating its methyl-alcoholic solution in small, coarsecrystals melting at 204208 C. with green coloration.

Analysis.-Calculated: C='73.9%, H=4.61%, N: 21.52%; found: C=73.78%,H:4.35%, N= 21.21%, O=0.77%.

The 1-amino-3-imino-4.S-benzodsoindolenine is difficultly soluble incold methanol, dissolves in methylalcoholic sodium hydroxide solutionwith weakly yellow coloration, however, precipitates again on addingwater because of the sodium salt being hydrolized. The product isdiflicultly soluble in acetone and comparatively diff ficultly solublein cold pyridine. It dissolves in dilute. acetic acid with yellowcoloration and precipitates as difiicultly soluble nitrate in yellowneedles by adding ammonium nitrate. It is soluble in dilute hydrochloricacid with yellow coloration but precipitates again immediately as yellowhydrochloride which is converted into colorless needles on boiling.

Example 36 11.0 parts of 3'.4-dicyano-(C) -phenyl-6-methyl-benzthiazolare introduced into a solution of 0.23 part of sodium in 55.4 parts ofmethanol diluted with 45.6 parts of benzene and stirred until thestarting product has almost completely been dissolved. Thereupon 4.1parts of ammonia (100%) dissolved in methanol are added and the solutionis kept at 35-40 C. until a test portion gives no longer a blue leucocompound. The crystalline precipitate is sucked off, washed with benzeneand ligroin and dried in vacuo.

Amino-imino-isoindoleninyl-methylbenzthiazol is obtained in a yield ofabout of the theoretical as greenish grey powder containing already inmethanol and of phthalocyanine and slightly dissolving in methanol andacetone. The product is soluble in dilute acetic acid with weakly yellowcoloration and precipitates as slightly soluble, weakly yellow nitratewhen adding ammonium. nitrate solution. The melting point of the productcon taining about /2 molecule of methanol is at about 262-264 C.

Example 37 18.96 parts of 4-methoxyphthalonitrile are introduced at 20C. into a solution of 0.69 part of sodium in 12.1 parts of methanoldiluted in 67.5 partsof benzene and stirred until the startingproducthas been dissolved with yellow coloration. Thereupon 12.24 parts ofammonia dissolved in methanol are added and stirring is continued untila test portion gives no stable blue leuco compound in dilute sodiumhydroxide solution and sodium hydrosulfite. The solution is thenconcentrated to a small volume in vacuo, the crystals precipitatingafter some time are sucked. ofi, washed with benzene and.

ligroin and dried in vacuo. S-(or 6-)methoxy-1-amino-3-imino-isoindo1enine is obtained in good yield in rodshaped colorlesscrystals becoming green at 180 C. and.

amino-S-imino-isoindolenine is obtained after removing a diflicultlysoluble by-product melting at 2172l8 C. and after concentrating thebenzene solution. The latter product has a melting point of 182-185 C.and exhibits similar properties as the above-said methoxy-compound.

Example 38 2.3 parts of sodium are dissolved in ethanol and the solutionis concentrated to 18-23 parts, stirred with 5264 parts of liquidammonia at about 30 C. and 12.8 parts of finely ground phthalonitrileare rapidly stirred in. The starting product is almost completelydissolved while extracting ammonia by vigorously boiling and1-ethoxy-3-imino-isoindolenine is then precipitated. The reactionproduct is isolated after 10 minutes by diluting the reaction mixturewith 100 parts of ice+water, sucking off, washing with water and dryingin vacuo at 3040 C., in a yield of 92% of the theoretical. 16 parts ofdiethoxy-imino-dihydro-isoindolenine thus obtained are heated with 36.4parts of concentrated aqueous ammonia on the water-bath. The product isdissolved within 3 minutes at 60-65 C. Traces of non-dissolved portionsare removed by filtering and the solution is chilled. A thick paste ofcolorless, almost rectangular small crystals, which are visible by meansof a microscope, is formed. The product is sucked oif, washed with somewater and dried. The yield amounts to 9 parts ofamino-imino-isoindolenine. By adding parts of ammonium nitrate to theaqueous filtrate and to the wash water further 4.7 parts of the slightlysoluble nitrate precipitate.

On replacing ammonia by methyl amine, dimethyliamine, other monoanddialkylamines or piperidine and morpholine the reaction yields a seriesof well-defined products wherein not only the alkoxybut also theimino-group is partly exchanged against alkylamino or alkyliminoradicals.

In the above reaction phthalonitrile may be replaced by3.4-dicyano-diphenyl or 4-methoxyphthalonitrile. In this case thereaction yields the corresponding nuclear substitutedl-amino-3-imino-isoindolenine derivatives.

Example 39 11 parts of diethoxy-imino-dihydro-isoindolenine are heatedwith 36 parts of aniline on the water bath as described in Example 49.The starting product dissolves within minutes at about 80 C. with deepyellow coloration and presently light yellow small crystals precipitate.After stirring at 95 C. for another minutes the solution is cooled downto C., sucked off, washed with methanol and dried. About 7 parts of1-anilino- 3-imino-isoir1dolenine forming greenish yellow, coarse smallcrystals melting at about 190207 C. with decomposition and orangecoloration are obtained. On acidifying the filtrate obtained asdescribed above with dilute hydrochloric acid a slightly soluble, full,yellow colored hydrochloride precipitates. According to analysis theproduct obtained is a monohydrochloride of 1-phenylamino-3-phenyliminoisoindolenine.

Example 40 7.1 parts of 4-methylphthalonitrile are introduced at 20 C.with stirring into a solution of 0.29 part of sodium in 5.05 parts ofmethanol diluted with 28.1 parts of benzene and stirring is continued at20 C. until the intensity of the yellow solution is not furtherincreased. Thereupon 1.28 parts of ammonia (100%) dissolved in methanolare added and stirring is continued until a test portion gives no longera blue leuco compound with dilute sodium hydroxide solution and sodiumhydrosulfite. The crystallized 5-(or6-)methyl-1-amino-3-iminoisoindolenine is sucked off and washed withbenzene and ligroin. The product yields colorless, full, long prismsbecoming green blue at 170 C., sintering at 181-182 C. and decomposingat 189-190 C. with blue coloration.

The portions of the base remaining dissolved in the '22 originalreaction liquid may be precipitated with formic acid as formate whichmay be purified by dissolving in water and precipitating with acetone.

Example 41 80.7 parts of a methanol solution containing about 8.0 partsof anhydrous sodium sulfide are mixed with 12.8 parts of finelydistributed phthalonitrile at 20 C. The temperature rises within 15minutes to 35-40" C. while the dinitrile dissolves with deepyellowtemporarily deep green-yellowcoloration. The solution is stirredfor another quarter of an hour and 20.0 parts of glacial acetic acid aregradually added drop by drop, the addition product formed therebyprecipitating in crystalline form with brownish coloration. The productis sucked off and washed with methanol. The yield amounts to 13.4 partsof a product which takes on heating a very dark color and sinters at220225 C. with decomposition. One part of a somewhat less pure productstill precipitates from the mother solution by adding water. Accordingto its chemical behavior, mode of origin and elementary analysis theproduct formed is the mercapto-imino-isoindolenine or in the tautomericform imino-thio-phthalimide. With aqueous sodium hydroxide solution anorange colored sodium salt is obtained being difficultly soluble whencold and dissolving on heating with orange coloration. The productdissolves in pyridine with red coloration and can be crystallized fromthis solvent. The pyridine salt first precipitating thereby decomposeson washing with methanol and shows again a light grey brown color.dilute hydrochloric acid a reddish grey salt is obtained whichtemporarily dissolves on heating, however, after some time deposits inreddish grey needles, presumably consisting of thiophthalimide andphthalimide.

With methanolic sodium hydrosulfide solution-prepared by cold saturationof a solution of anhydrous NazS in methanol with HzS and filtering offthe precipitated sulfur-the mercapto-imino-isoindolenine describedherein is obtained on heating within a short time. In this case theproduct deposits directly on cooling as orange colored sodium salt.

On boiling the mercapto-imino-isoindolenine in nitrobenzene for a shorttime blue needles with a metallic lustre of metal-free phthalocyanineprecipitate, hydrogen sulfide escaping thereby.

16.2 parts of mercapto-imino-isoindolenine in 147 parts of pyridine aremixed with 12 parts of ammonium nitrate with stirring. By gently heatingon the water bath the starting product dissolves within 10 minutes, analmost colorless compound precipitating from the red brown solution in acrystalline form. After stirring for half an hour at C. the solution issucked off, the precipitate is washed with pyridine until clear, washedagain with water and dried. The almost colorless residue crystallizesfrom dilute aqueous ammonia in colorless needles and dis plays allproperties of the amino-imino-isoindolenine nitrate.

Example 42 1000 parts of acetamide and 128 parts of phthalonitrile areintroduced into a solution of 150 parts of potassium hydroxide in 400parts of technical methanol. The solution thus obtained is heated forsome time at 70 C. and is stirred still hot into a mixture of 1000 partsof ammonium nitrate and ice. The precipitatingamino-imino-isoindolenine-nitrate is sucked off, washed with water anddried. By boiling out with benzene and acetone the reaction product isobtained in good purity.

Example 43 parts of amino-imino-isoindolenine are stirred with 500 partsof aniline at 5060 C., the base slowly dissolving andanilino-imino-isoindolenine or its tautomeric forms crystallizingthereby while gaseous ammonia escapes.

With

After hours the solution is cooled with ice, suckedoft, tl 1 eprecipitate is washed with methanol or acetone and dried. The lightyellow product melting at 208 C. is obtained in analytically pure form.The yield amounts to 95% of the theoretical.

On carrying out the reaction. in boiling methanol the quantity ofaniline may be. reduced to about 1-00 parts.

Example 44 145 parts of amino-imino-isoindolenine and 200 parts ofaniline are heated with stirring.

The monosubstitution product temporarily crystallizing and redissolvingon further heating is initially formed with splitting oif of ammonia.The temperature is then raised to 200 C. and the solution is kept atthis temperature until the splitting oil of ammonia is practicallycomplete. The initially clear melt has now become deep yellow;l-phenylamino-3-phenylimino-isoindolenine crystallizes on cooling.Isolation is achieved by diluting the melt chilled to about 50 C. withbenzene or acetone to double the volume, cooling with ice and furtherdiluting with benzine.

Ifhe pure base is colorless, dissolves in alcohols, acetone and benzeneand melts at 130 C. with yellow coloration and maybe distilled at165-168 C. under 5 mm. pressure Without decomposition. The salts of thebase are deep yellow colored. The product is obtained in a quantitativeyield.

The addition product of 1 mol of aniline to 1 mol of phenylamino 3phenylimino-isoindolenine temporarily crystallizes under the saidconditions. This product melts at 78-49 C. and splits off again theadded aniline at 90-100 C.

Example 45 20 parts of amino-imino-isoindolenine and 30 parts ofo-anisidine are heated with stirring as fast as possible in View of theactive splitting off of ammonia and the solution is kept at 150 C. forminutes, the base charged being initially dissolved in anisidine.Presently the reaction product crystallizes already at the reactiontemperature. The reaction mixture is then cooled, stirred with methanol,sucked oifj when ice-cold, the precipitate is washed with methanol anddried. o-Methoxy-anilinoimino-isoindolenine or its tautomersrespectively are obtained in analytically pure form. The light yellowproduct melts at 195-200 C.

Example 46 parts. of amino-imino-isoindolenine and 30 parts. of m-anjsidine are heated. with stirring at 150 C. until, after 30- to 50 minutessplitting off of ammonia is practically comp e ecold, deep yellow meltis diluted with methanol and; the deep yellow chloride ofm-methoXyanilino-mmethoxy-phenylimino-isoindolenine is precipitated bymeans of hydrochloric acid.

Example 47 5 parts-of amino-imino-isoindolenine are gently heated withvexcess cyclohexoxypropylamine with stirring. At- 7080 C; ammonia readilyescapes. Thereupon the mixture is dissolved" in. water and weaklyacidified with nitric acid. Crystallization of cyclohexoxypropylaminocyclohexoxy propylimino isoindoleninenitrate is completed by. addingasolution of ammonium nitrate. On heating in glycol with copper acetatethe product gives an easily, soluble, brightly orange colored oppero pExample 48 are suspended in parts of methanol at-room tempera-. ture and24 parts of monoethanolamine are rapidly added, the starting productbeing immediately dissolved. thereby. Impurities in the solution aresucked ofi as fast as possible and the filtrate. is stirred for sometime. OxethylaminooXethylimino-isoindolenine obtained in a quantitativeyield is colorless and melts at 196 C.

In form of the free base the product is insoluble in most customarysolvents when cold.

The reaction may also be accomplished in aqueous solution.

Example 49 20 parts of amino-imino-isoindolenine are reacted with 40parts of p-nitraniline in boiling glacial acetic acid.

After the starting product has initially been dissolved 1.4nitrophenylarnino 3.4" nitrophenyl imino isoindolenine precipitates inlight yellow small needles melting at 3l13l2 C.

The product yields a sodium salt crystallizing from aqueous methanol inlong, deep red needles which is hydrolizedagain with much water.

Example 5 0 22 parts of l-anilino-3-imino-isoindolenine (melting. point207 C.) are introduced into 69 parts of boiling tetraline. The solutionis rapidly orange colored with the evolution of ammonia. Boiling isstopped after 3-4 minutes, the solution: is cooled to about 100 C. andsucked oil. The residue consists of a small quantity (about 0.8 part) offinely crystallized, metal-free phthalocyanine.

On diluting; the brown orange colored filtrate with one and a half timesthe quantity of methanol weakly orange colored. needles precipitate-After cooling the precipitate is sucked 0E, washedwith methanol anddried. The yield amounts to 6.5 parts. On boiling. for a longer time theyield of the orange red product is reduced. The product is readilysoluble inv hot benzene and crystallizes by adding methanol in felted,brownish red needles melting at 187 C. According to analysis (C=79.15,H=4'.6, N=l5.75%) the reaction product is a condensation productconsisting of 2 mols of l-anilino-3-imino-isoindolenine having split 0Eone mol of NH3 or of 3 mols'of aminophenyl-imino-phthalimide havingsplit off 2 mols of NH3..

The orange redcolored product melting at 187 C. is slightly. soluble inmethanol, however, immediately dissolves with deep orange yellowcoloration by adding sodium hydroxide solution. By adding some water andhydrosulfite to; the mixture an initially green, thereafter blue,vat-like solution is obtained which is decolorized on heating.

Example 51' 24 parts of 1-oxethyl-amino-3-oxethyl-imino-isoindolenine(prepared according to Example. 48) are stirred with 100 parts' ofacetic anhydride, the temperature being allowed to raise to 50 C. After:one hour the excess anhydride is decomposed by adding ice, common saltsolution is added to the clear solution in equal volume and theprecipitated l-acetoXethyl-amino-3acetoXethyl-irnino-isoindolenine-hydrochloride is-isol'ated byconventional-methods. The reaction product is obtained as colorless,readily soluble salt.

Example 52 13 parts of amino-imino-isoindolenine and 30 parts ofanesthesin are dissolved in 200parts of anhydrous ethanol and thetemperature is raised to C. while distilling the alcohol. The reactionis completed within a short time. After stirring with cold alcohol,sucking-off and drying 19 parts of analytically pure, light-yellowl-(p-carbethnxy-phenyll-aminoa-imino-isoindolenine melting at 20 partsof technical amino-imino-isoindolenine-nitrate Z 198-200? C; areobtained.

Example 53 Example 54 80 parts of phthalonitrile and 97 parts of3-chloro aniline are reacted in a methylate solution consisting of 2parts of sodium and 50 parts of methanol at temperatures between 30 and45 C. Already after 30 minutes the reaction product begins tocrystallize from the clear solution. After 10-20 hours isolation isaccomplished in the usual manner. 115-120 parts of pure, light-yellow1-(3- chlorophenyl)-amino 3 imino isoindolenine melting at 214 C. areobtained.

Example 55 2 parts of sodium are dissolved in 150 parts of anhydrousmethanol and in this solution 80 parts of phthalonitrile and 100 partsof 4-chloro aniline are caused to react. 105-110 parts of light-yellow1-(4'-chlorophenyl)-amino- B-imino-isoindolenine melting at 206 C. areobtained.

Example 56 78 parts of 1-(3'-chlorophenyl)-amino-3-imino-isoindolenine(prepared according to Example 54) and 38 parts of 3-chloro aniline areheated in 100 parts of xylene at 150 C. for 7 hours, filtered at 100 C.and stirred when cold; the yellow crystallizate is sucked oil. whenice-cold, washed with benzine and dried. 91 parts of 1(3'-chlorophenyl)amino-3-(3-chlorophenyl)-iminoisoindolenine melting at150 C. are obtained.

Example 57 78 parts of 1-(4'-chlorophenyl)-amino-3-imino-isoindolenine(prepared according to Example 55), 39 parts of 4-chloro aniline and 100parts of xylene are heated under reflux to the boil for 5-7 hours, allreactants being dissolved thereby. 96 parts of 1 (4'-chlorophenyl)-amino 3-(4-chlorophenyl) -imino-isoindolenine melting at 150 C. areobtained.

Example 58 2 parts of sodium, 80 parts of 4-anisidine, 80 parts of Vphthalonitrile are successively dissolved in 100 parts of anhydrousmethanol, the temperature being allowed to raise up to 40-50 C. After 24hours the crystallized product is sucked oli when ice-cold, washed anddried. 128 parts 1 (4 methoxy-phenyl)-amino-3-imino-isoindoleninemelting at 190-195 C. are obtained.

Example 59 81 parts of 1 (4 methoxyphenyl)-amino-3-iminoisoindolenine(prepared according to Example 58), 41 parts of 4-anisidine in 100 partsof xylene are heated to the boil for 6-8 hours and then cooled withstirring. 85- 90 parts ofl-(4-methoxyphenyl)-amino-3-(4"-methoxyphenyl)-imino-isoindolenine areobtained. The yellow product melts at 150-155 C.

Example 60 26 tered off, washed with methanol and acetone and dried. Theyield amounts to 160 parts by weight.

Example 61 2 parts of sodium are dissolved in 700 parts by volume ofmethanol while stirring at room temperature. 70 parts of3.4-dicyano-pyridine are introduced and a weak stream of gaseous ammoniais passed through the solution at 20-30 C. The solution becomes yellowat the beginning and, after about /2 hour, a grey crystallineprecipitate consisting of 6-(or 5-)aza-1-amino-3-imino-isoindolenineforms to an increasing extent, which is suction filtered after about 24hours, washed with acetone and ether and dried. The yield amounts to 65parts.

Example 62 19.2 parts of 4-ethoxy phthalic anhydride (M. P. 119- 120)are introduced at C. with stirring into a homo-' geneous melt of 32.4parts of urea and 19.2 parts of ammonium nitrate with the addition of0.03 part of ammonium molybdate. By heating the melt foams between andC., a brown-yellow, almost clear melt forms at 174-176 C. After about 2hours stirring a light crystalline precipitate forms almostinstantaneously and the mixture becomes viscous. The mixture is dilutedby quickly running in 100 parts of ice-cold water, stirred until ahomogeneous paste has formed, filtered 01f, washed with water and dried.22.6 parts of almost colorless nitrate of 1 amino 3 imino-S-(or6-)-ethoxy-isoindolenine, which corresponds to 89 per cent of theory areobtained. The product decomposes at about 247 C. It yields the free basewith aqueous caustic soda solution. The base decomposes at about 175 C.with the formation of a green melt.

In analogous manner the nitrate of 1-amino-3-imino-5- (or6)methoxy-isoindolenine is obtained from 4-methoxyphthalimide (M. P. ofthe pure product 216 C. uncorrected) or 4-methoxy-phthalic anhydride (M.P. 98-99" C.). The reaction product shows a decomposition point of242-245 C. and dissolves in Water somewhat more easily than theanalogous product containing no methoxy group.

Example 63 8 parts of 4-methylmercapto phthalimide (M. P. 212- 213 C.)are introduced into a mixture of 12 parts of urea, 8 parts of ammoniumnitrate, 9 parts of nitrobenzene, 0.1 part of ammonium molybdate at 130C. and the mixture is gradually heated to -175 C. The solution which isclear at the beginning becomes yellowbrown on heating and fine,orange-yellow colored crystals precipitate after heating for about 3hours. The reaction mass becomes soon very viscous; therefore it isexpedient to dilute the mixture with 20 parts of nitrobenzene. After areaction time of 3 hours the mixture is diluted with methanol aftercooling to 80 C. and suction filtered in the hot state. The reactionproduct is washed with methanol and water and thereafter dried. Thenitrate obtained in good yield crystallizes in long lemon-yellow needleswhich melt at 236 C.

By reacting the nitrate with the calculated amount of caustic sodasolution in a suspension of methanol and water 1-amino-3-imino-5- (or6-)methylmercaptoisoindolenine melting at 207-208 C. is obtained. Thecrystallized, weakly yellowish base dissolves in dilute acetic acid withan intensive orange-yellow coloration.

Example 64 A moderate stream of ammonia is passed over a suspension of53.5 parts of phthalonitrile in 64 parts of a solution of ammonia inmethanol containing about 12.5 parts of ammonia and 0.65 part of 19.25per cent of a solution of caustic soda in methanol. The suspension isgradually heated to 60 C. and stirred at this temperature for about 1 /2hours. The phthalonitrile dissolves after about 1% hours, and l-amino3-imino-isoindolenine (or its methanol addition compound) precipitatesin coarse heavy crystals.

A small sample of the reaction mixture in a mixture of pyridine andwater gives a blue leuco compound with dilute caustic soda solution andsodium hyposulfite.

After about 1 /2 hours this leuco compound of a sample has disappearedalmost completely; 0.20 part of glacial acetic acid is then added andstirring is continued at 60 C. for about /2 hour while passing overammonia until no blue leuco compound is any longer visible.

When carrying out the reaction on a large scale production it is notnecessary to precipitate the 1-amino-3-iminoisoindolenine in pure form.In this case it is sufiicient to evaporate the reaction mixture todryness in vacuo. About 62.1 parts of an almost colorless to faintlygreenish product containing about 99.6 per cent of pure product, whichcorresponds to a yield of about 93 per cent of theory, are thusobtained.

Example 65 20.4 parts of 3.4-dicyano-diphenyl and 24.4 parts of a 10.5per cent of solution of ammonia in methanol are introduced into thesolution of 0.45 part of caustic soda in 48 parts of methanol and themixture is stirred at 4050 C. The dinitrile dissolves during 4-6 hours.The solution is neutralized with 0.68 part of glacial acetic acid andconcentrated to a small volume. The resulting 1- amino-3=imino-5-(or6-)phenyl-isoindolenine can be isolated by stirring the concentratedmethanol solution with about 80 parts of toluene and subsequentlyevaporating the-solvent in vacuo. The product is obtained as loosepowder in a yield of over 90 per cent.

Example 66 aqueous solution in long, colorless needles in form of ahydrate which can be dried at low temperature. The hydrate thus obtainedcan further be dried at 90-95 C.

without the danger of saponification, the anhydrobase being thusobtained. The pure anhydrobase melts at about 194-196" C. with greencoloration and evolution of ammonia. By prolonged heating the aqueoussolution having a strongly bitter taste the product is saponified toform mono-imino-phthalimide and, finally, phthalimide with the evolutionof ammonia.

Upon addition of nitrate-, phosphate-, sulfiteor perchlorateions thecorresponding colorless, very difficultly soluble salts precipitate incrystals in an almost quantitative yield.

The anhydrobase and its hydrate easily dissolve in methanol already inthe cold but are very slightly soluble in ether, acetone, benzene andcyclohexane, even in the heat. The base quickly dissolves in higherboiling solvents such as nitrobenzene and dichloro benzene and even inpyridine with green coloration and evolution of ammonia and partialformation of metal free phthalocyanine. By mixing thel-arnino-3-imino-isoindolenine with glycol while stirring a crystallizedaddition product, which is more fully descrbed in Example 17, isobtained. By heating the addition product with metallic salts, particularly in the presence of solvents, under suitable, weakly reducingconditions the corresponding metal phthalocyamines are obtained with thesplitting oil of ammonia, mostly in a very good yield and even at waterbath temperatures.

calculated for found CzzHisOsNa Percent Percent C=74.95 0 74.77 H= 4.20H= 4.28 N=11.65 N=l1.89

Example 67 10 parts of 1-amino-3-imino-isoindolenine and 19 parts ofN-amino-piperidinc-hydrochloride are dissolved in 150 parts of methanoland left standing at-room temperature until the intensity of the yellowcoloration no longer increases. By introducing 500 parts of water withstirring, the reaction product precipitates in light yellow crystals.The yield amounts to per cent of theory. The base,C1sH2sN5=l-(1-piperidyl-amino) 3 (1" piperidlyimino)-isoindole'nine isobtained analytically pure from pure starting materials. The base can bepurified by recrystallizing from gasoline or another organic solvent, orby dissolving in an alcohol and precipitating with water.- The basedissolves in dilute acids but not in pure water.

Example 68 Example 69 In 25 parts of methanol are dissolved 4 parts ofl-amino- 3-imino-isoindolenineand 9 parts of a paratiin amine of thestatistical molecular Weight 194 which is obtained from the so-calledfirst runnings of fatty acids via the ketones obtainable therefromaccording to conventional methods. By stirring the solution at 20 C. fortwo hours, the amino group of the isoindolenine derivative is exchangedfor the paraflin amine. The reaction product which crystallizes isfiltered off at 0 C., Washed with some cold methanol and dried. 3.2parts of paraflin-aminoimino-isoindolenine is obtained which, accordingto analysis, has the statistical summation formula CzoflHsazNs The basecan be recrystallized from light gasoline.

' 7 Example 70 20 parts of 1-paraiiin-amino-3-imino-isoindolenine, 20parts of ethanolamine, and 20 parts of glacial acetic acid aresuccessively dissolved in 160 parts of methanol and the solution isstirred at room temperature. After 30 minutes1-hydroxyethyl-amino-3-hydroxyethyl-imino-isoindolenine begins tocrystallize. Stirring is continued for another hour and the reactionproduct which is obtained in a quantitative yield is isolated byfiltering, washing with 'water and drying.

Example 71 p 20 parts of 1-anilino-3-anilo-isoindolenine-hydrochlorideare suspended in parts of methanol and 10 parts of 'ethanolamine areadded. The solution'which is dark Example 72 18 parts of hexamethylenediamine and 20 parts of phthalonitrile are reacted in the sodiummethylate solution prepared from 0.5 part of sodium and 80 parts ofmethanol at 4050 C. An amino-imino-isoindolenine derivative(C3HsN3(CH2)6NH2), which is substituted with one amino-hexamethyleneradical is formed. The reaction mixture is diluted with another 160parts of methanol as soon as the reaction, which is exothermic at thestart, is complete.

The solution is further stirred at room temperature for a prolongedperiod, at least 24 hours. The product slowly crystallizes in a yield of34 parts which, according to analysis, represents N .N-cyclohexa-methylene-1- amino-S-imino-isoindolenine formed byintramolecular amine exchange reaction to which two molecules ofmethanol are attached.

+2CHaOH F 210218 C.

The product can be recrystallized from methanol (dissolution andcrystallization proceeds very slowly); by boiling with acetic acidanhydride and pyridine the product yields the acetyl derivativeCsH4Ns(CH2)sOCOCH3 (M. P. 154 C.) which is liberated from methanol.

Example 73 15 parts of 1-an1ino-3-imino-isoindolenine, and 40 parts of4-amino-azo-benzene are heated in 200 parts of xylene until no ammoniais any longer split oif. When cooling the dark orange colored1-benzene-azo-anilino-3-benzeneazo-anil-isoindolenine crystallizes ingood yield. The product is isolated by filtering and washing with coldmethanol.

Example 74 Example 75 24 parts of 3.4-dicyano-diphenyl are reacted with20 parts of 4-amino-diphenyl in a solution of 0.5 part of sodium in 160parts of methanol.

1 (4' phenyl) anilino 3 imino (or 6-) phenyl isoindolenine obtained in aquantity of 27.5 parts is heated to the boil in 13 parts of4-amino-diphenyl in 200 parts of xylene whereby 50 parts of xylene areslowly filtered off. When cooling and/ or diluting with a mixture ofpetroleum and ether the dark-yellow colored 1' (4' phenyl) anilino 3 (4"phenyl) anilo 5 (or 6-) phenyl isoindolenine crystallizes. The productis isolated by filtering andwashing with petroleum and ether.

Example 76 20 parts of 1-amino-3-imino-4-(or 7-)aza-isoindoleninenitrate are dissolved in 50. parts of Z-amino-ethanol and 30 parts ofmethanol, filtered, diluted with another 40 parts of methanol andstirred at room temperature for 2 to 3 hours.1-hydroxyl-ethyl-amino-3-hydroxy-ethylimino-4-(or 7-)aza-isoindoleninecrystallizes in good yield. The product dissolves in alcohol, water andmixtures of acetone and water and is almost insoluble in dry acetone.

On replacing ethanolamine by aniline the correspondingphenyl-substituted isoindolenine derivative is obtained in good yields.By replacing ethanolamine by piperidine the reaction yields the1-piperidino-3-irnino-4-(or 7-)azaisoindolenine.

Example 77 8.8 parts of 1-thiomethyl-3-imino-isoindolenine (weaklycream-colored needles which melt at 102103 C. with evolution of gas andformation of a blue melt) are boiled with reflux with 8 parts ofammonium nitrate in 80 parts of methanol. Already after some minutes agreenishgrey, slightly soluble product precipitates and methylmercaptane escapes. The product (about 5 parts) which is isolated afterone hours heating under reflux, cooled to 40 C., suction filtered andwashed with methanol, substantially represents the nitrate of1-amino-3-iminoisoindolenine. By dissolving the product in cold dilutecaustic soda solution, filtering oil the non-dissolved, coloredcontaminations and precipitating the clear, almost colorless filtratewith glacial acetic acid with the addition of some ammonium nitrate, thenitrate of l-amino- 3-imino-isoindolenine is obtained in colorless,sandy-crystalline form. (M. P.=293294 C.) By replacing ammonia byaniline or ethanolamine the correspondingly substituted1-amino3-imino-isoindoleniue derivatives are obtained in good yields.

1thiomethyl-3-imino-isoindolenine is obtained by finely grinding 16.2parts of imino-thio-phthalimide (prepared according to Example 41) with320 parts of water, heating the suspension formed to 60 C. and mixingwith 25 parts by Volume of caustic soda solution (40 per cent). Thesolution thus obtained is quickly filtered and quickly cooled to 20 C.by addition of ice. By stirring the resulting clear, brown-yellowsolution with 15 parts of dimethyl sulfate at room temperature weaklyyellowish colored crystals precipitate after a short time. Theprecipitate is filtered off, washed with cold water and dried in theexsiccator. The yield amounts to 12 parts. The crude1-thio-methyl-3-imino-isoindolenine is unstable on exposure to highertemperatures and light. It melts at about 90 C. with evolution of gasand formation of a dark green-blue colored melt. By dissolving the meltin methanol at a max. temperature of 40 C. and slowly diluting withwater the product is obtained in creamcolored needles of the meltingpoint l02l03 C. after green coloration from C. By heating thethio-methyl ether in nitrobenzene and even in glacial acetic acidmetalfree phthalocyanine is obtained.

Example 78 A weak current of ammonia is passed over a suspension of 0.28part of methanolic caustic soda solution (19.25%) 19.8 parts ofmethanolic ammonia (corresponding to 3.75 parts of ammonia) and 7.19parts of 4-ethoxy-phthalonitrile (prepared by splitting oil water from4-ethoxy-phthalamide, M. P. 133-l34 C.) until the4-ethoxy-phthalonitrile has dissolved and 4-ethoxyphthalonitrile is nolonger precipitated from a sample of the suspension on diluting withwater and some drops of caustic soda solution. Thereupon 0.08 part ofglacial acetic acid is added and ammonia is passed over the solution foranother /2 hour. By evaporating the solution 5-(or6-)ethoxy-1-amino-3-imino-isoindolenine is obtained as light crystallinepowder which contains only small quantities of sodium acetate and can beemployed immediately for further reaction. The crude product becomesgreenish at 166-174" C. and decomposes at 176l77 C. with foaming. It iseasily soluble in methanol and dilute acetic acid and difiicultly inacetone. The yellow solution in hydrochloric acid is quickly decolorizedby hydrolysis of S-(or 6-)ethoXy-1-amino-3-imino-isoindolenine. Theslightly soluble nitrate of the base can be precipitated by mixing themethanolic aqueous solution with ammonium nitrate solution and Weaklyacidifying with acetic acid. The nitrate which can advantageous- 1y beutilized for producing the pure base is weakly lemonyellow colored. Itbecomes darker at 240 C. and decomposes at 244-245 C. with foaming.

By decomposing the nitrate suspended in methyl alcohol with thecalculated amount of caustic soda solution and diluting the resultingsolution with water, the pure base is obtained in small, coarse crystalswhich decom pose at 179-180 C. By replacing ammonia by primary orsecondary amines the correspondingly substituted isoindoleninederivatives are obtained.

Example 79 When replacing in the preceding example4-ethoxyphthalonitrile by the equivalent amount of4-phenoxyphthalonitrile (prepared by splitting olf water from 4- phenoxyphthalamide, M. P. 101-102 C.) a'solution of 5- (or6-)phenoxy-1-amino-3-imino-isoindolenine is obtained. By evaporating thesolution the base remains behind as a brittle, yellow colored mass whichcan easily be pulverized. The mass is easily soluble in methanol,difiicultly soluble in acetone and shows properties similar to theethoxy compound described in the preceding example. The slightly solublenitrate of the base, which is strongly lemon-yellow colored, becomesdark at temperatures above 250 C. and decomposes at 264265 C. withfoaming. The base prepared from the nitrate melts at 94-96 C. to form adark green liquid which decomposes at 101102 C. with foaming.

The syntheses described in the foregoing paragraphs B, C and D areequivalent to each other, i. e. it is possible to produce any1-amino-3-imino-isoindolenine de rivative directly from dinitrile byaddition of an amine as Well as by exchange of the alkoxy or amino groupin the corresponding l-alkoxyor l-amino-3-imino-isoindoleninederivatives for the same amine. In the foregoing examples the processesaccording to paragraphs B, C and D are interchangeable as will beapparent to anyone skilled in the art. Therefore it is unnecessary tospecifically describe each of these processes for each and everyisoindolenine derivative hereinbefore described, the disclosure of oneprocess constituting also a full disclosure of the other possiblemethods. Furthermore each 1- amino-3-imino-isoindolenine derivativeobtainable by the method of production according to paragraphs A and Emay also be obtained by the processes described in paragraphs B, C andD.

We claim:

1. The process for the production of l-amino-S-iminoisoindoleninederivatives which comprises reacting at temperatures up to about 160 C.an aromatic dinitrile with a nitrogen containing compound which, in theform of its free base, is one of the general formula wherein R1 and R2stand for radicals selected from the group consisting of hydrogen,alkyl, cycloalkyl, aralkyl, aryl having at most three rings and SO2aryl, and R1+R2 stand for a radical selected from the group consistingof the divalent radicals -(CHz) 5 and (CH2)2O(CH2)2 both free valencesbeing attached to the nitrogen atom.

2. A process as claimed in claim 1 which comprises carrying. out thereaction in an inert organic solvent.

3.. A. process. as claimed, in claim 1 which comprises carrying out thereaction under superatmospheric pressure up to about 120 kg./cm. withammonia as nitrogen containing compound.

4. A process as claimed in claim 1 which comprises carrying out thereaction at temperatures up to about C. in an inert organic solventselected from the group consisting of primary saturated aliphaticalcohols and mixtures thereof with aromatic hydrocarbons, in thepresence of an alkali compound selected from the group consisting ofalkali metal hydroxides, earth alkali metal hydroxides, alkali metalalcoholates, and alkaline earth metal alcoholates.

5. A process as claimed in claim 1 which comprises carrying out thereaction in the presence of urea and wherein the nitrogen containingcompound is selected from the group consisting of ammonium nitrate,ammonium phosphate and ammonium chloride.

6. A process as claimed in claim 1 wherein the nitrogen containingcompound is arnmonia, produced intermediately by carrying out thereaction at temperatures up to about 100 C. in formamide with a compoundselected from the group consisting of alkali metal amides, alkali metalalcoholates, and alkaline earth metal hydroxides.

7. A process as claimed in claim 1 which comprises carrying out thereaction in an aliphatic alcohol containing at least one CHzOH-group andin the presence of a substance selected from the group consisting ofheavy metals and heavy metal salts.

8. As new compounds l-amino-3-iminoisoindolenine derivatives of thegeneral formula 10. The compounds of claim 8 wherein Z, together withthe two carbon atoms to which it is joined, represents 11. The compoundsof claim 8 wherein Z, together with the two carbon atoms to which it isjoined, represents with the two carbon atoms to which it is joined,represents 34 References Cited in the file of this patent UNITED STATESPATENTS Baumann et a1. July 13, 1954 OTHER REFERENCES Franklin: NitrogenSystem of Compounds, p. 267, Reinhold Pub. C0rp., N. Y. (1935).

1. THE PROCESS FOR THE PRODUCTION OF 1-AMINO-3-IMINOISOINDOLENINEDERIVATIVES WHICH COMPRISES REACTING AT TEMPERATURES UP TO ABOUT 160*C.AN AROMATIC DINITRILE WITH A NITROGEN CONTAINING COMPOUND WHICH, IN THEFORM OF ITS FREE BASE, IS ONE OF THE GENERAL FORMULA